Development of a Novel Nanoarchitecture of the Robust Photosystem I from a Volcanic Microalga Cyanidioschyzon merolae on Single Layer Graphene for Improved Photocurrent Generation.

Here, we report the development of a novel photoactive biomolecular nanoarchitecture based on the genetically engineered extremophilic photosystem I (PSI) biophotocatalyst interfaced with a single layer graphene via pyrene-nitrilotriacetic acid self-assembled monolayer (SAM). For the oriented and stable immobilization of the PSI biophotocatalyst, an His6-tag was genetically engineered at the N-terminus of the stromal PsaD subunit of PSI, allowing for the preferential binding of this photoactive complex with its reducing side towards the graphene monolayer. This approach yielded a novel robust and ordered nanoarchitecture designed to generate an efficient direct electron transfer pathway between graphene, the metal redox center in the organic SAM and the photo-oxidized PSI biocatalyst. The nanosystem yielded an overall current output of 16.5 µA·cm-2 for the nickel- and 17.3 µA·cm-2 for the cobalt-based nanoassemblies, and was stable for at least 1 h of continuous standard illumination. The novel green nanosystem described in this work carries the high potential for future applications due to its robustness, highly ordered and simple architecture characterized by the high biophotocatalyst loading as well as simplicity of manufacturing.

Synthesis and performance of antifouling and self-cleaning polyethersulfone/graphene oxide composite membrane functionalized with photoactive semiconductor catalyst.

This study was performed to synthesize membranes of polyethersulfone (PES) blended with graphene oxide (GO) and PES blended with GO functionalized with photoactive semiconductor catalyst (TiO2 and ZnO). The antifouling and self-cleaning properties of composite membranes were also investigated. The GO was prepared from natural graphite powder by oxidation method at low temperature. TiO2 and ZnO nanopowders were synthesized by anhydrous sol-gel method. The surface of TiO2 and ZnO nanopowders was modified by a surfactant (myristic acid) to obtain a homogeneously dispersed mixture in a solvent, and then GO was functionalized by loading with these metal oxide nanopowders. The PES membranes blended with GO and functionalized GO into the casting solution were prepared via phase inversion method and tested for their antifouling as well as self-cleaning properties. The composite membranes were synthesized as 14%wt. of PES polymer with three different concentrations (0.5, 1.0, and 2.0%wt.) of GO, GO-TiO2, and GO-ZnO. The functionalization of membranes improved hydrophilicity property of membranes as compared to neat PES membrane. However, the lowest flux was obtained by functionalized membranes with GO-TiO2. The results showed that functionalized membranes demonstrated better self-cleaning property than neat PES membrane. Moreover, the flux recovery rate of functionalized membranes over five cycles was higher than that of neat membrane.

Evaluating the simultaneous electrochemical determination of antineoplastic drugs using LaNiO3/g-C3N4@RGH nanocomposite material.

A novel electrochemical sensor based on LaNiO3/g-C3N4@RGH nanocomposite material was developed to simultaneously determine Ribociclib (RIBO) and Alpelisib (ALPE). Ribociclib and Alpelisib are vital anticancer medications used in the treatment of advanced breast cancer. The sensor exhibited excellent electrocatalytic activity towards the oxidation of RIBO and ALPE, enabling their simultaneous detection. The fabricated sensor was characterized using various techniques, including energy dispersive X-ray (EDX), Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XR), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS), which confirmed the successful synthesis of the LaNiO3/g-C3N4@RGH composite material. Electrochemical characterization revealed enhanced conductivity and lower resistance of the modified electrode compared to the bare electrode. The developed sensor exhibited high repeatability, reproducibility, stability, and selectivity toward RIBO detection. Furthermore, the sensor displayed high sensitivity with low detection limits of 0.88 nM for RIBO and 6.1 nM for ALPE, and linear ranges of 0.05-6.2 µM and 0.5-6.5 µM, respectively. The proposed electrochemical sensor offers a promising approach for simultaneously determining RIBO and ALPE in pharmaceutical formulations and biological samples with recovery data of 98.7-102.0 %, providing a valuable tool for anticancer drug analysis and clinical research.

Investigation of the antifouling properties of polyethersulfone ultrafiltration membranes by blending of boron nitride quantum dots.

This study aims to investigate the modification of polyethersulfone (PES) membrane with boron nitride quantum dots (BNQD) for improving the antifouling performance. The composite membranes were synthesized by blending different amounts of BNQD (0.50, 1.00, and 2.00 wt.%) into PES with the non-solvent induced phase separation (NIPS) method. UV-vis absorption, X-ray diffraction (XRD), and transmission electron microscopy (TEM) were used to characterize BNQD. Moreover, porosity, pore size, contact angle, permeability, bovine serum albumin (BSA) rejection, and antifouling properties were determined for composite membranes. The enhanced biological activity of BNQD was investigated based on antioxidant, antimicrobial, anti-biofilm, bacterial viability inhibition, and DNA cleavage studies. The BNQD showed 19.35 % DPPH radical scavenging activity and 76.45 % ferrous ion chelating activity at 500 mg/L. They also exhibited good chemical nuclease activity at all concentrations. BNQD had moderate antibacterial activity against all tested microorganisms. Biofilm inhibition percentage of BNQD was determined as 82.31 % at 500 mg/L. Cell viability assay demonstrated that the BNQD showed strong cell viability inhibition 99.9 % at the concentration of 1000 mg/L. The porosity increased from 56.83 ± 1.17%-61.83 ± 1.17 % while BNQD concentration increased from 0 to 2.00 wt%. Moreover, the hydrophilicity of BNQD nanocomposite membranes also increased from 75.42 ± 0.56° to 65.34 ± 0.25°. The mean pore radius is far slightly changed from 16.47 ± 0.35 nm to 19.16 ± 0.22 nm. The water flux increased from 133.5 ± 9.5 L/m2/h (for pristine membrane) to 388.6 ± 18.8 L/m2/h (for PES/BNQD 2.00 wt% membrane). BSA flux increased from 38.8 ± 0.9 L/m2/h to 63.2 ± 2.7 L/m2/h up to 1.00 wt% amount of BNQD nanoparticles.

Imidazole substituted Zinc(II) phthalocyanines for co-catalyst-free photoelectrochemical and photocatalytic hydrogen evolution: influence of the anchoring group.

Novel zinc phthalocyanine derivatives, ZnPc-1 and ZnPc-2, consisting of one and four imidazole units, respectively, have been synthesized and utilized as panchromatic photosensitizers for photocatalytic and photoelectrochemical H2 evolution. The effect of the imidazole-anchoring group on the photocatalytic H2 production has been compared with ZnPc-3, which possesses a carboxylic acid unit as the anchoring group. ZnPc-1/TiO2 shows the best photoactivity with the highest H2 evolution rate of 0.4006 mmol g-1 h-1, which is much higher than that of ZnPc-2/TiO2 and ZnPc-3/TiO2 (0.3319 mmol g-1 h-1 and 0.3555 mmol g-1 h-1, respectively). After 20 h of irradiation, ZnPc-1 produces an H2 production rate of 3.4187 mmol g-1 with a turnover number (TON) of 14863 and a solar-to-hydrogen energy (STH) conversion efficiency of 1.03%, without using a co-catalyst.

Molecular mechanism of direct electron transfer in the robust cytochrome-functionalised graphene nanosystem.

Construction of green nanodevices characterised by excellent long-term performance remains high priority in biotechnology and medicine. Tight electronic coupling of proteins to electrodes is essential for efficient direct electron transfer (DET) across the bio-organic interface. Rational modulation of this coupling depends on in-depth understanding of the intricate properties of interfacial DET. Here, we dissect the molecular mechanism of DET in a hybrid nanodevice in which a model electroactive protein, cytochrome c 553 (cyt c 553), naturally interacting with photosystem I, was interfaced with single layer graphene (SLG) via the conductive self-assembled monolayer (SAM) formed by pyrene-nitrilotriacetic acid (pyr-NTA) molecules chelated to transition metal redox centers. We demonstrate that efficient DET occurs between graphene and cyt c 553 whose kinetics and directionality depends on the metal incorporated into the bio-organic interface: Co enhances the cathodic current from SLG to haem, whereas Ni exerts the opposite effect. QM/MM simulations yield the mechanistic model of interfacial DET based on either tunnelling or hopping of electrons between graphene, pyr-NTA-M2+ SAM and cyt c 553 depending on the metal in SAM. Considerably different electronic configurations were identified for the interfacial metal redox centers: a closed-shell system for Ni and a radical system for the Co with altered occupancy of HOMO/LUMO levels. The feasibility of fine-tuning the electronic properties of the bio-molecular SAM upon incorporation of various metal centers paves the way for the rational design of the optimal molecular interface between abiotic and biotic components of the viable green hybrid devices, e.g. solar cells, optoelectronic nanosystems and solar-to-fuel assemblies.

Enhancement of direct electron transfer in graphene bioelectrodes containing novel cytochrome c553 variants with optimized heme orientation.

The highly efficient bioelectrodes based on single layer graphene (SLG) functionalized with pyrene self-assembled monolayer and novel cytochromec553(cytc553)peptide linker variants were rationally designed to optimize the direct electron transfer (DET) between SLG and the heme group of cyt. Through a combination of photoelectrochemical and quantum mechanical (QM/MM) approaches we show that the specific amino acid sequence of a short peptide genetically inserted between the cytc553holoprotein and thesurface anchoring C-terminal His6-tag plays a crucial role in ensuring the optimal orientation and distance of the heme group with respect to the SLG surface. Consequently, efficient DET occurring between graphene and cyt c553 leads to a 20-fold enhancement of the cathodic photocurrent output compared to the previously reported devices of a similar type. The QM/MM modeling implies that a perpendicular or parallel orientation of the heme group with respect to the SLG surface is detrimental to DET, whereas the tilted orientation favors the cathodic photocurrent generation. Our work confirms the possibility of fine-tuning the electronic communication within complex bio-organic nanoarchitectures and interfaces due to optimization of the tilt angle of the heme group, its distance from the SLG surface and optimal HOMO/LUMO levels of the interacting redox centers.

Subphthalocyanine-sensitized TiO2 photocatalyst for photoelectrochemical and photocatalytic hydrogen evolution.

A series of SubPcs comprising a carboxylic acid anchoring group at the peripheral (SubPcs 1, 2) or axial position (SubPc 3) were synthesized and used as sensitizers for photocatalytic H2 production, for the first time. SubPc 3/TiO2 shows the best photocatalytic activity with a hydrogen evolution rate of 1396 µmol h-1, which is much higher than that of SubPcs 1 and 2 (771 and 658 µmol g-1, respectively). This work clearly shows that considering their optical and redox properties, SubPcs are promising candidates for light-driven water splitting systems.

Preparation and evaluation of effect on Escherichia coli and Staphylococcus aureus of radiolabeled ampicillin-loaded graphene oxide nanoflakes.

Ampicillin is a one of effective antibiotics against Gram-positive and Gram-negative bacteria. This study aimed to label ampicillin-loaded graphene oxide nanoflake (AMP-GO) with 99m Tc and evaluate of its in vitro binding to Staphylococcus aureus and Escherichia coli. Firstly, ampicillin was loaded into graphene oxide nanoflake prepared. AMP-GO was characterized by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscope (SEM) techniques, and the amount of loaded ampicillin onto GO was determined by UV-Vis absorption spectroscopy. AMP and AMP-GO were labeled with 99m Tc using stannous chloride reducing agent. Labeling efficiency of 99m Tc-AMP-GO was found to be 97.66 ± 2.06%. 99m Tc-AMP-GO has higher binding efficiencies to both S. aureus and E. coli than 99m Tc-AMP. 99m Tc-AMP-GO could be promising candidate as agent infection nuclear imaging. Furthermore, in vivo studies of 99m Tc-AMP-GO with infected rats are planned to be performed.

Synergetic effects of Fe3+ doped spinel Li4Ti5O12 nanoparticles on reduced graphene oxide for high surface electrode hybrid supercapacitors.

In this work, reduced graphene oxide (rGO) based electrode materials were developed to achieve a hybrid supercapacitor (SC) function. Therefore, several synthesis methods were developed to prepare a cost effective and environmentally friendly rGO. Additionally, to maintain the high surface area, spinel lithium titanate (sLTO) nanoparticles (NPs) were synthesized and deposited on the rGO surface to inhibit the restacking of the rGO layers on graphite. Furthermore, the adequate Fe-doping of sLTO increased the ionic conductivity and the intercalation capacity, which is necessary for a SC performance. The sLTO/rGO-composites were electrochemically analysed by chronopotentiometry and electrochemical impedance spectroscopy (EIS) to determine the stability during charge/discharge cycling and the capacity, respectively. To overcome the drawback of LTO's low conductivity values, its value has been drastically increased by Fe-doping. The results demonstrated the remarkable cycling performance of the Fe:LTO/rGO composite as well as a higher capacity compared to LTO/rGO and pure rGO-electrodes. The thermal stability, degradation and weight loss of the sLTO/rGO in the temperature range between 20 °C and 800 °C were investigated by thermogravimetry (TG)/DTA. As a conclusion, it can be stated that, increasing the ionic conductivity by Fe-doping drastically increases the hybrid capacity of the SC electrodes.

High-Capacitance Hybrid Supercapacitor Based on Multi-Colored Fluorescent Carbon-Dots.

Multi-colored, water soluble fluorescent carbon nanodots (C-Dots) with quantum yield changing from 4.6 to 18.3% were synthesized in multi-gram using dated cola beverage through a simple thermal synthesis method and implemented as conductive and ion donating supercapacitor component. Various properties of C-Dots, including size, crystal structure, morphology and surface properties along with their Raman and electron paramagnetic resonance spectra were analyzed and compared by means of their fluorescence and electronic properties. α-Manganese Oxide-Polypyrrole (PPy) nanorods decorated with C-Dots were further conducted as anode materials in a supercapacitor. Reduced graphene oxide was used as cathode along with the dicationic bis-imidazolium based ionic liquid in order to enhance the charge transfer and wetting capacity of electrode surfaces. For this purpose, we used octyl-bis(3-methylimidazolium)diiodide (C8H16BImI) synthesized by N-alkylation reaction as liquid ionic membrane electrolyte. Paramagnetic resonance and impedance spectroscopy have been undertaken in order to understand the origin of the performance of hybrid capacitor in more depth. In particular, we obtained high capacitance value (C = 17.3 µF/cm2) which is exceptionally related not only the quality of synthesis but also the choice of electrode and electrolyte materials. Moreover, each component used in the construction of the hybrid supercapacitor is also played a key role to achieve high capacitance value.

A nanoscale bio-inspired light-harvesting system developed from self-assembled alkyl-functionalized metallochlorin nano-aggregates.

Self-assembled supramolecular organization of nano-structured biomimetic light-harvesting modules inside solid-state nano-templates can be exploited to develop excellent light-harvesting materials for artificial photosynthetic devices. We present here a hybrid light-harvesting system mimicking the chlorosomal structures of the natural photosynthetic system using synthetic zinc chlorin units (ZnChl-C6, ZnChl-C12 and ZnChl-C18) that are self-aggregated inside the anodic aluminum oxide (AAO) nano-channel membranes. AAO nano-templates were modified with a TiO2 matrix and functionalized with long hydrophobic chains to facilitate the formation of supramolecular Zn-chlorin aggregates. The transparent Zn-chlorin nano-aggregates inside the alkyl-TiO2 modified AAO nano-channels have a diameter of ∼120 nm in a 60 µm length channel. UV-Vis studies and fluorescence emission spectra further confirm the formation of the supramolecular ZnChl aggregates from monomer molecules inside the alkyl-functionalized nano-channels. Our results prove that the novel and unique method can be used to produce efficient and stable light-harvesting assemblies for effective solar energy capture through transparent and stable nano-channel ceramic materials modified with bio-mimetic molecular self-assembled nano-aggregates.